Linear polyesters of 4,4&#39; dichlorocarbonyldiphenylsulfone and aromatic dihydroxy compounds and their method of preparation



United States Patent 3,536,665 LINEAR POLYESTERS 0F 4,4 DICHLOROCAR- BONYLDIPHENYLSULFONE AND AROMATIC DIHYDROXY COMPOUNDS AND THEIR METH- 0D 0F PREPARATION Edward W. Pietrusza, Morristown, and Jack R. Pedersen,

Parsippany, N.J., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed May 25, 1967, Ser. No. 641,129 Int. Cl. C08g 17/03, 17/08, 33/10 US. Cl. 260-49 4 Claims ABSTRACT OF THE DISCLOSURE This spcification discloses a new class of linear aromatic polyesters from 4,4-dichlorocarbonyldiphenylsulfone and aromatic dihydroxy compounds and a method for preparing them. Copolyesters and terpolyesters wherein other acid components and/or mixtures of dihydroxy compounds are employed are also disclosed. The polymers of the invention are prepared by reacting the starting materials in a solvent in the presence of a catalyst under anhydrous conditions at normal pressures and moderate temperatures. The polymers are stable at high temperatures and are useful in the formation of fibers, films, molded articles, and the like, particularly for high temperature applications.

Glycol esters of 4,4-dicarboxydiphenylsulfone are known to form polymers which have higher melting points than the corresponding glycol esters of other aryl dicarboxylic acids, such as the glycol esters of terephthalic acid, using conventional condensation polymerization techniques. Such methods employ high temperatures and/ or vacuum distillation to bring about condensation between the glycol reactant and the dicarboxylic acid reactant. The condensation reaction between 4,4'-dicar boxydiphenylsulfone or its ester and an aromatic dihydroxy compound does not occur readily using conventional condensation techniques. Due to the high melting points of the polymers, very high temperatures must be employed which promote degradation of the resultant polyesters and prevent the formation of polymers having high molecular weights. The stringent reaction conditions also add substantially to the costs of these processes.

Linear aromatic polyesters have been disclosed by Conix et al., U.S. Pat. 3,028,364, issued Apr. 3, 1962. In that disclosure, the acid chloride of 4,4-dicarboxydiphenylsulfone was dissolved in a solvent and reacted with an aqueous solution of the sodium salt of a bisphenol. While that polymerization process can be conducted at moderate temperatures, it does not lend itself to the preparation of sulfone polyesters of high molecular weights such as are required for the preparation of fibers and the like.

It is a principal object of the present invention to provide linear aromatic sulfone polyesters.

It is another object to provide novel polyesters from 4,4-dicarboxydiphenylsulfone and an aromatic dihydroxy compound.

It is a further object to provide copolymers and terpolymers from 4,4'-dicarboxydiphenylsulfone and aromatic dihydroxy compounds.

It is another object to provide novel polyesters, copolyesters, and terpolyesters derived from 4,4'-dicarboxydiphenylsulfone and an aromatic dihydroxy compound having high molecular weights suitable for the preparation of fibers, films, and molded articles.

Patented Oct. 27, 1970 "ice It is another object to provide a process for the preparation of high molecular weight polyesters derived from 4,4-dicarboxydiphenylsulfone and aromatic dihydroxy compounds at moderate temperatures and normal pressures.

Further objects will become apparent from the following detailed description thereof.

We have discovered that linear high molecular weight aromatic polyesters derived from 4,4-dichlorocarbonyldiphenylsulfone and aromatic dihydroxy compounds can be prepared readily at moderate temperatures and normal pressures by reacting them in equimolar amounts in 3. catalyzed solution under anhydrous conditions. The polyesters of the invention have high glass transition temperatures, high flow temperatures, and high decomposition temperatures, and are useful for the production of fibers,

films, coatings, and molded articles, particularly for hightemperature applications. In addition to the polyesters of the invention, a wide variety of copolyesters and terpolyesters can be prepared in similar manner from mixtures of starting materials. For example, 4,4'-dichlorocarbonyldiphenylsulfone can be admixed with one or more different aromatic or aliphatic dicarboxylic acid chlorides and/or the aromatic dihydroxy reactant can be admixed with one or more different aromatic or aliphatic dihydroXy compounds.

According to the process of the invention, 4,4'-dichlorocarbonyldiphenylsulfone, alone, or in admixture with other dicarboXylic acid chlorides, is reacted in a catalyzed solution with an aromatic dihydroXy reactant. The mixture is reacted at least until evolution of hydrogen chloride has ceased. The polymer product is then isolated. By varying the conditions of time and temperature of reaction and concentrations and types of starting materials, a wide range of polyesters, copolyesters and terpolyesters can be prepared having determinable molecular weights and properties.

Equimolar amounts of the 4,4'-dichlorocarbonyldiphenylsulfone reactant and the dihydroxy reactant are preferred in our process since the presence of an excess of either reactant will act as a terminator for the polymerization reaction resulting in the formation of low molecular Weight polyesters.

The solvent should be a solvent for both the 4,4-dichlorocarbonyldiphenylsulfone reactant and the dihydroxy reactant and preferably for the resultant polyester, although this is not required. In general, aromatic hydrocarbons and halogenated aromatic hydrocarbons are solvents which may be employed in the process of the invention, including benzene, toluene, o-Xylene, m-xylene, p-Xylene, p-cymeme, diphenylmethane, 1,3,5-triethylbenzene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, and the like. In general, the use of higher boiling solvents will result in the formation of high'molecular weight polymers.

Elfective catalysts include certain metals and their salts such as magnesium metal, zinc metal, aluminum metal and cuprous chloride. The catalysts Which are useful are quite specific since similar metals and salts including nickel metal, copper metal and zinc chloride were found to be ineffective as catalysts. Additional metals and metallic salts which are effective as catalysts in the process of the present invention can be determined by one skilled in the art. The catalyst concentration can be from 0.01 to 2.00 wt. percent. In the absence of an elfective catalyst, only low molecular weight polyesters are obtained. Particularly outstanding results were obtained with magnesium metal catalyst.

The polymerization reaction proceeds readily at the reflux temperature of the reaction mixture which depends upon the boiling point of the solvent employed during polymerization. In general, the rate of polymerization will increase at higher temperatures of reaction.

The time required for the formation of high molecular Weight polyester will vary depending upon the temperature of the reaction, the purity of the reactants and the choice of catalysts. The reactants and the solvent must be essentially free from impurities and water which cause degradative side reactions and chain termination and prevent the formation of high molecular weight polymer. Increasing the time of reaction increases the molecular weight of the resultant polymer with accompanying increases in glass transition temperature, flow temperature, and decomposition temperature.

4,4-dichlorocarbonyldiphenylsulfone can be prepared by reaction of 4,4'-dicarboxydiphenylsulfone with a solution of phosphorous pentachloride and phosphorous oxychloride. The excess oxychloride is distilled 011, and the product can be isolated by distillation or recrystallization from a suitable solvent.

Acyl chloride derivatives of other dicarboxylic acids can be added as part of the acid chloride reactant. Such dicarboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, a-ethyl suberic acid, sebacic acid, dodecanedioic acid, a,a-diethyl adipic acid and the like. Subsituted aliphatic acids such as ortho-, metaor paraphenylene diacetic acid and o-phenylene acetic-B-propionic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 4,4'diphenyldicar- 'boxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenylmethanedicarboxylic acid, 2,2-(4,4-dicarboxydiphenyl)propane, 4,4-dicarboxydiphenyldichloromethane, and the like.

The aromatic dihydroxy compounds suitable for use in the invention include aromatic diols and bisphenols wherein each reactive hydroxy radical is directly attached to a benzene ring. Suitable compounds, for example, inelude and its derivatives having the formula wherein each node represents a tetravalent carbon atom, A, A, X and X represent hydrogen substitutes in a position ortho to the phenolic hydroxy group, A and A are alkyl radicals having from 1 to 3 carbon atoms, X and X are halogens independently selected from the group consisting of chlorine and bromine; n and n are integers from 0 to 2; p and p are integers from 0 to 2; the sum 4 of n and p are less than 3 and the sum of n and p are less than 3.

These compounds, hereinafter referred to as Kepone bisphenols, can be prepared by reacting a C Cl O ketone (l,la,3,3a,4,5,5,5a,5b,6 decachlorooctahydro 1,3,4 metheno-2H-cyclobuta[cd] -pentalene-2-one) or a hydrate thereof with the corresponding phenol compound having a free para position at an elevated temperature in the presence of an acid catalyst. A suitable process for preparing such Kepone bisphenols employing a boron trifluoride catalyst is disclosed in US. Pat. 3,370,086; and a process employing a sulfonic acid catalyst is disclosed in U.S. Pat. 3,420,894.

Mixtures of more than one aromatic dihydroxy compound can be employed, including mixtures containing for example 1,3-dihydroxybenzene and 1,4-dihydroxybenzene or an aliphatic dihydroxycompound can be substituted in part for the aromatic dihydroxy compound. Suitable aliphatic dihydroxy compounds include the polymethylene glycols having from 2 to 10 carbon atoms such as ethylene glycol, 1,5-pentanediol, 1,10-decanediol and other glycols of this series, branched chain glycols such as 2,2-dimethyl-1,3-propanediol, 2-methyl-1,5-pentanediol and the like and carbocyclie glycols such as 1, di(hydroxyethyl)benzene, 1,4 bis(2'-hydroxyethyl)-2,5- dichlorobenzene and the like. Derivatives of any of the above glycols bearing one or more substituents which will not interfere with the formation of high molecular weight linear polyesters, such as nitro-substituted glycols, can also be employed.

The polymer product can be isolated in any convenient manner such as will be known to one skilled in the art. One convenient method is to filter off the catalyst and pour the reaction mixture into a nonsolvent for the polymer. The precipitated polymer can be further purified by washing and drying to remove solvent.

The polymers prepared in accordance with the invention are high melting, thermoplastic materials of high molecular weights suitable for use as fibers, films, and other shaped articles which may be formed from the polymer by conventional techniques such as molding, extrusion, and the like. These polymers are also useful as coatings which offer protection against the effects of elevated temperature.

The following examples are given to further illustrate the invention, but it is to be understood that the invention is not meant to be limited to the details disclosed therein.

In the examples all parts are by weight unless otherwise noted. The reduced viscosity of the polymers was determined as a 0.52% by weight solution in m-cresol at 25 C. Glass transition temperatures, referred to as Tg and decomposition temperatures were determined by differential thermal analysis except when otherwise noted. The tensile property measurements reported were carried out using an Instron tensile tester operated at a constant speed crosshead separation of 0.5 inch per minute.

EXAMPLE 1 228 parts of 2,2-bis(4-hydroxyphenyl) propane, 340 parts of 4,4'-dichlorocarbonyldiphenylsulfone, 2.4 parts of powdered magnesium and 2500 parts by volume of monochlorobenzene were charged to a reaction vessel fitted with a magnetic stirrer and a reflux condenser. The reaction mixture was refluxed for 9.5 hours under nitrogen when evolution of hydrogen chloride had ceased. The resultant mixture was filtered through glass wool and the filtrate poured into 7500 parts by volume of isopropanol. The solid polymer product was ground, Washed with isopropanol and dried.

The polymeric product had a flow point of 310330 C.

The reduced viscosity was 0.41. The Tg was 220 C. and the polymer decomposed at 430-450 C. A good film was cast from a monochlorobenzene solution.

Infrared analysis confirmed the structure for a linear izing carbon and drying in a vacuum oven, 68 parts of polymer having recurring units of the formula 4,4-dichlorocarbonyldiphenylsulfone, 4.8 parts of powr r i r 1 L ll 411. J

EXAMPLE 2 dered magnesium and 2000 parts by volume of freshly 228 parts of 2,2 biS(4 hydroXypheny1)propane 343 distilled o-dichlorobenzene were charged to a vessel as parts of 4,4-dichlorocarbonyldiphenylsulfone, 2.5 parts m Eliample 1 and refluxeq for 15 hours The of powdered magnesium and 3000 parts by volume of 10 solution was poured into isopropanol. The precipitated freshly distilled o-dichlorobenzene were charged to a vespolymer 9 extracted Wlth hot lsopmpanol sel as in Example 1 and refluxed for 10 hours. Some prodtered and dncd a Vacuum ovenuct had precipitated out and was redissolved on heating. The Polymer had a reduced Viscosity of It Was a The solution was filtered and poured into isopropanol high melting material having a flow PQiIlt when the product precipitated out. It was ground and O The decomposition temperature was 450 C. A self-suswashed with isopropanol and dried at 120 C. for 3 days. taining film was cast from o-dichlorobenzene.

A polymer having a reduced viscosity of 1.06, softening Infrared analysis confirmed the structure for a polymer point of 330-340 C., and Tg of 200 C. was obtained. having recurring units of the formula The decomposition temperature was 450 C. EXAMPLE A clear, slightly yellow sheet was molded from the polymer at 340 C. and tons pressure for one minute. 154.3 parts of Kepone bisphenol, 53.4 parts of 2,2- A self-sustaining film was cast from a 4% solution in -hy r yph y )p p 160-5 Parts of dimethylformamide, chlorocarbonyldiphenylsulfone (mol ratio 0.5 :0.5 :1), 1.2 EXAMPLE 3 parts of powdered magnesium and 3000 parts by volume of o-dichlorobenzene were charged to a vessel as in Ex- 346 parts of 1,4-bis(p-hydroxycumyl)benzene, 343 ample 1 and refluxed for 18 hours. The solution was fil- Parts of 4,4'-dichlOfOcafbonyldiphenylsulfone, Parts Of 40 tered and poured into isopropanol. The precipitated prodpowdered magnesium and 6500 parts by volume of freshly uct was washed with isopropanol and dried.

distilled o-dichlorobenzene were charged to a vessel as in The reduced viscosity of the polymer was 0.54. A clear Example 1 and refluxed for 10 hours. The solution was film was cast from o-dichlorobenzene. The polymer had poured into isopropanol and the precipitated product a ver high softening point of over 360 C., a Tg of washed and dried. 220 C., and decomposition temperature of 415 C.

The reduced viscosity of the polymer was 0.57. The

polymer had a softening point of 290-325 C. and de- EXAMPLES 6-12 composition point of 480-500 C. The glass transition temperature was 226 C. A series of copolymers was prepared following the The structure was confirmed as having recurring units Procedure given in Example Varying the diacid f h f l ponent by admixing 4,4-dichlorocarbonyldiphenylsulfone o o 0 CH OH (H n n 3 r a w -o 0-o o- L 0 (in CH J The polymer was compression-molded (at 340 C.) into with equimolar amounts of an aliphatic or aromatic dithin Clear Sheets having high Strength acid and by admixing the aromatic dihydroxy compound EXAMPLE 4 with equimolar amounts of a different aromatic or ali- 132 parts of Kepone bisphenol, purified by recrystal- Phatic dihydroxy compound. The examples are sum- 60 lizing from aqueous methanol, treating with decolormarized in the table below:

Decom- Flow position Reduced temp., Tg, temp., Example Diacid components Dlhydroxy component viscosity 7 0. 0. C.

6 4,4-dichlorocarbonyl-diphenylsulione and adipyl chlor' e. 2,2-bis(4-hydroxyhenyl)propane 00.99 265-295 400 7 4,4f-lich]orocarbonyl-diphenylsultone and sebaeyl ehIodo 10.02 235-265 133 400 11 8. V V 8 4,4ilrliicliorocarbonyl-dlphenylsulfone and isophtha10yl-- do 00.26 235-260 196 450 c or e. V 9 4Aggliehlorocarbonyl-diphenylsulfone and adipyl chlo- 1,4-bis(p-hydroxycumyDbenzene 00.96 240-280 160 400 r e. 10 4,4-diehlorocarbonyl-diphenylsulfone and sebacyl eh1odo 00.70 220-240 132 425 ride. 11.-.... 4,4'-dichlorocarbonyl-diphenylsulfone 2,2l-liiG-hydgloxlyphenyl)propane and 00. 59 220-240 155 350 exane o. 12. do 2,2-b1s(4-hydroxyphenyl)propaue and 00.20 -240 200 495 1,4-bis (p-hydroxyeumybbenzene.

It is apparent that a wide range of copolymers and terpolymers can be obtained in similar manner with a Wide range of glass transistion temperatures and flow 8 D882-64T with a testing speed of 0.05"/min. The excellent tensile properties of these polyesters are given in the table below:

Te 2% secant st Polymer of temp, Elongation, strength, modulus, Example Solvent 0. percent p.s.i. p.s.i

1 Mnochl0r0benzene 23 18 11,500 114, 000 23 16 10,800 107, 000 2 Dimethylformamide 175 9 4,500 79,000 200 10 4, 000 01, 000 23 16 10,500 129, 000 4 o-Dichlorobenzcnc 195 9 4,200 75,900 200 9 4, 300 64, 009 23 17 10, 900 118, 000 23 13 0, 400 95, 000 23 13 10,900 123, 000 23 11 9, 200 95, 900

temperatures. In general the addition of an al1phat1c re- EXAMPLE 17 actant lowers the glass transition temperature, flow temperature, and decomposition temperature obtained for wholly aromatic polyesters having similar molecular weights.

EXAMPLE 13 456 parts of 2,2-bis(4-hydroxyphenyl) propane, 236 parts of 1,6-hexanediol, 406 parts of terephthaloyl chloride, 686 parts of 4,4'-dichlorocarbonyldiphenylsulfone (equimolar quantities), 8 parts of powdered magnesium and 10,000 parts by volume of o-dichlorobenzene were charged to a vessel as in Example 1 and refluxed for hours. The solution was filtered and poured into isopropanol. The precipitated product was washed with isopropanol and dried.

The reduced viscosity of the polymer was 0.4. The polymer had a softening point of 200 C. and a Tg of 115 C.

EXAMPLE 14 Following the procedure given in Example 5, various copolymers were prepared from 4,4-dichlorocarbonyldiphenylsulfone, adipyl chloride and 2,2-bis(4-hydroxyphenyl)propane. The results are given below where it can be seen that flow temperatures, glass transition temperatures and decomposition temperatures increase with incr asing 4,4-dichlorocarbonyldiphenylsulfone content.

M01 Decompercent Flow position Mol percent 4,4'-dichloroadipyl Tg, temp., temp., carbonyldiphenylsulfone chloride 0. 0. C.

EXAMPLE 15 Reduced viscosity Tg, C.

EXAMPLE 16 Clear films of several polyesters were cast from solution. The films were dried at 90110 C. under reduced pressure, cut into tensile impact specimens according to ASTM D1822-61T, type L, and tested as per ASTM test Compression molding Pres- Percent Temp, sure, Time, water 0. tons min. uptake EXAMPLE 18 Composites of glass cloth and the polyesters were prepared by dissolving the polyesters in o-dichlorobenzene,

applying the solutions to the glass cloth, and evaporating the solvent. Excellent strengths were maintained at elevated temperatures as shown by the table below:

Ultimate Weight Test Ultimate tensile 2% secant Polymer of percent temp, elongation, strength, modulus, Example of glass C. percent p.s.i. p.s.l.

23 5 10, 400 1. Glass control 175 9 4, 300

We claim:

1. An essentially linear, fiberand film-forming polyester of 4,4-dich10rocarbonyldiphenylsulfone and 2,2-bis (4 hydroxyphenyl) 1,1a,3,3a,4,5,5,5a,5b,6-decachlorooctahydro-1,3,4-metheno-2H-cyclobuta[cd] pentalene.

2. A process for preparing essentially linear fiber-and film-forming polyesters which comprises reacting a mixture of reactants comprising 4,4 dichlorocarbonyldiphenylsulfone and an aromatic dihydroxy compound wherein each hydroxy radical is attached directly to an aromatic ring carbon atom under anhydrous conditions in an inert solvent for said reactants and at the reflux temperature of the solvent in the presence of a catalyst selected from the group consisting of magnesium metal, zinc metal, aluminum metal and cuprous chloride and recovering the product.

3. The process of claim 2 wherein the dihydroxy compound is 2,2-bis(4-hydroxyphenyl)propane or 1,4-bis(phydroxycumyl) benzene.

4. The process of claim 2 wherein the dihydroxy com pound is 2,2-bis(4'-hydroxyphenyl)-1,la,3,3a,4,5,5,5a,5b,

6 decachlorooctahydro 1,3,4 metheno-ZH-cyclobuta 3,374,202 3/1968 Schwarz. [cd]pentalene. 3,398,121 8/1968 Oxenrider et 211. References Cited 3,438,938 4/1969 Oxenrider et a1.

UNITED STATES PATENTS FOREIGN PATENTS 3,110,547 11/1963 Emmett. 5 3,160,602 12/1964 Kantor 6161. 1511030 12/1962 France 3,216,970 11/ 1965 COmX- WILLIAM H. SHORT, Primary Examiner 3,223,752 12/1965 Tate e161. 3,251,805 5/1966 Schnell et a1. QUAST Asslstant Exammer 3,271,365 9/1966 Parham. 10 3,297,633 1/1967 Hindersinn 61.61. US 3,350,354 10/1967 Watson. 117-126; 260-32.6; 33.8, 47, 75 

